Nitrogen- and Oxygen-Containing Porous Ultrafine Carbon Nanofiber: A Highly Flexible Electrode Material for Supercapacitor

doi:10.1016/j.jmst.2016.03.014

Abstract

Abstract:

Herein, we report a simple and effective preparation of ultrafine CNFs (u-CNFs) with high surface area via electrospinning of two immiscible polymers [polyacrylonitrile (PAN) and poly(methyl methacrylate) (PMMA)] followed by calcination at high temperature in an inert atmosphere. Various electrospinning conditions were optimized in detail. Four different kinds of PAN/PMMA ratios (10/0, 7:3, 5:5 and 3:7) were chosen and found that the PAN/PMMA ratio of 3:7 (PAN/PMMA-3:7) is the optimum one. BET analysis showed the specific surface area of the u-CNFs-3:7 was 467.57 m²/g with an excellent pore volume (1.15 cm³ g^-1) and an average pore size (9.48 nm): it is about 25 times higher than the conventional CNFs (c-CNFs). TEM and FE-SEM images confirmed the ultrafine structure of the CNFs with a thinner fiber diameter of ~50 nm. The graphitic nature and atomic arrangement of the u-CNFs were investigated by Raman and XPS analyses. For the supercapacitor application, unlike the common electrode preparation methods, the u-CNFs-3:7 was used without any activation, chemical or mechanical modifications. The u-CNFs-3:7 showed a better specific capacitance of 86 F/g in 1 mol/L H₂SO₄ when compared to pure CNFs. The excellent physicochemical properties make the u-CNFs-3:7 an alternative choice to the existing CNFs for the supercapacitors.

Key words: Carbon fiber, Porosity, Electron microscopy, Surface analysis, Supercapacitor

Wei Kai, Kim Kyu-Oh, Song Kyung-Hun, Kang Chang-Yong, Soon Lee Jung, Gopiraman Mayakrishnan, Kim Ick-Soo. Nitrogen- and Oxygen-Containing Porous Ultrafine Carbon Nanofiber: A Highly Flexible Electrode Material for Supercapacitor[J]. J. Mater. Sci. Technol., 2017, 33(5): 424-431.

Figures/Tables 12

Fig. 1. Schematic diagram for the preparation of u-CNFs.

Fig. 2. Surface tension of PAN and PMMA solutions with different concentrations.

Fig. 3. Viscosity of PAN/PMMA solutions with different mixing ratios and concentrations.

Fig. 4. FE-SEM images of electrospun PAN/PMMA nanofibers with different mixing ratios: (a) PAN/PMMA-7:3 (8 wt%, 10 wt%, 12 wt%, 14 wt% and 16 wt%), (b) PAN/PMMA-5:5 (10 wt%, 12 wt%, 14 wt%, 16 wt% and 18 wt%), (c) PAN/PMMA-3:7 (14 wt%, 16 wt%, 18 wt%, 20 wt% and 22 wt%).

Fig. 5. Microscope photos of PAN/PMMA solutions with different mixing ratios: (a) 7:3, (b) 5:5, (c) 3:7.

Fig. 6. FE-SEM images of (a) CNFs, (b) CNFs-7:3, (c) CNFs-5:5 and (d) u-CNFs-7:3.

Fig. 7. TEM images of (a) CNFs, (b) CNFs-7:3, (c) CNFs-5:5, (d, e, f and g) u-CNFs-7:3 and the histogram of fiber diameter distribution (h) of u-CNFs-7:3.

Fig. 8. (a) Raman spectra of CNFs, CNFs-3:7, CNFs-5:5 and u-CNFs-7:3. (b) C 1s, (c) N 1s and (d) O 1s XPS peaks of CNFs, CNFs-7:3, CNFs-5:5 and CNFs-3:7.

Fig. 9. (a) Deconvoluted C 1s and (b) N 1s XPS peaks of u-CNFs-3:7. (c) Digital photo of CNFs, CNFs-7:3, CNFs-5:5 and u-CNFs-3:7, and (d) bending test showing the excellent flexibility of the u-CNFs-3:7.

Fig. 10. (a) Nitrogen adsorption-desorption isotherms and (b) pore size distribution of CNFs, CNFs-7:3, CNFs-5:5 and u-CNFs-3:7.

Table 1. BET surface area and pore properties of CNFs, CNFs-7:3, CNFs-5:5 and u-CNFs-3:7

Sample	[as, BET] (m² g^-1)	Pore properties
Sample	[as, BET] (m² g^-1)	[Vm] (cm³g^-1)	Pore volume (cm³g^-1)	Pore size (nm)
CNFs	352.13	80.90	0.26	2.95
CNFs-7:3	349.35	78.26	0.37	6.27
CNFs-5:5	405.56	90.07	0.98	9.24
u-CNFs-3:7	467.57	107.43	1.15	9.84

Fig. 11. (a) Cyclic voltammetry results for the u-CNFs-3:7 at different scan rates in 1.0 mol/L H2SO4 and (b) specific capacitance for the u-CNFs-3:7 and CNFs at different scan rates in 1.0 mol/L H2SO4.

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